Ni base alloy pipe stock and method for manufacturing the same

ABSTRACT

A Ni base alloy pipe stock having a chemical composition comprising, by mass %, C≦0.04%, Si≦0.50%, Mn: 0.01 to 6.0%, P≦0.03%, S≦0.01%, Cr: 15 to 30%, Ni: more than 45% to not more than 60%, Mo: 0 to 18%, W: 0 to 36%, with Mo(%)+0.5W(%): more than 1.5% to not more than 18%, Cu: 0.01 to 1.5%, Al≦0.01% and N: 0.0005 to 0.20%, and the balance substantially being Fe, with 1380−5000P−100S−4400C≧1300, Ni+10(Mo+0.5W)+100N≦200, (Ni−50)+10(N−0.1)−2(Cr−25)−5(Mo+0.5W−6)+12≧0, can be manufactured into a seamless pipe by use of a Mannesmann piercing and rolling mill because of its excellent inner surface properties. The resulting seamless pipe has excellent mechanical properties and moreover has excellent corrosion resistance in a sour gas environment, and thus, the Ni base alloy pipe stock can be used as a pipe stock for oil country tubular goods and line pipes and further as a pipe stock for various structural members of nuclear power plants and chemical industrial plants.

This application is a continuation of the international applicationPCT/JP2005/011993 field on Jun. 29, 2005, the entire content of which isherein incorporated by reference.

TECHNICAL FIELD

The present invention relates to Ni base alloy pipe stocks, methods formanufacturing the same, and Ni base alloy seamless pipes which aremanufactured using such pipe stocks. More specifically, the presentinvention relates to Ni base alloy pipe stocks, being obtained bypiercing and rolling by use of a Mannesmann piercing and rolling mill(hereinafter referred also to as “piercer”), which are excellent incorrosion resistance in an environment which is rich in corrosivesubstance such as carbon dioxide, hydrogen sulfide, S (sulfur) andchloride ion (hereinafter referred to as a “sour gas environment”) inaddition to excellent mechanical properties, such as strength andductility, and suitable for pipe stocks for oil country tubular goodsand line pipes, and further suitable for pipe stocks for variousstructural members of nuclear power plants and chemical industrialplants, and also to the manufacturing methods thereof, and Ni base alloyseamless pipes which are manufactured using the above-mentioned pipestocks.

BACKGROUND ART

While development of oil wells and gas wells is expanding on a globalscale after the first oil shocks, increased demand for energy indeveloping countries increasingly forces deepening of oil wells and gaswells and the drilling of wells in a sour gas environment with furthersevere corrosiveness.

With such increased severity in the oil well and gas well environments,for example, various Ni base alloys, higher in strength than ever beforeand excellent in corrosion resistance, as shown in the Patent Documents1 and 2, and further a super austenitic stainless steel as shown in thePatent Document 3, have been developed and practically used.

However, economic globalization, such as corporate marriage orreorganization which has rapidly progressed on a world scale through thetermination of the cold war between the East and the West, theintegration of the EU, or the like intensifies the price competitionamong companies. Consequently, in the development of oil wells and gaswells, higher efficiency and lower cost are in demand in addition toensuring safety.

Increased productivity of oil or gas can be attained by using largediameter pipes. Moreover, the further use of strong material enablesreduction in the wall thickness of the pipes, resulting in saving ofmaterial cost. Therefore, as a steel stock for pipes used in oil wellsand gas wells, a material cost saving and having a higher strength thanever before is requested. The enlargement of the diameter of the pipesis also important.

On the other hand, in the development of oil wells and gas wells,reduced costs can be attained by using inexpensive material which hassufficient strength and corrosion resistance.

The Patent Document 4 thus discloses a “high Cr-high Ni alloy, excellentin stress corrosion cracking resistance”, which is enhanced ineconomical property by reducing the Mo content in alloys which contain,by weight %, 20 to 35% of Cr and 25 to 50% of Ni.

If piercing and rolling by a piercer can be adapted, pipe stocks forlarge diameter pipes or sufficiently long pipes can be efficientlymanufactured at a low cost on an industrial scale.

The Patent Document 5 therefor discloses a “method for piercing aseamless tube of hard-to-work material with piercer”, which is intendedto provide a manufacturing method of seamless pipes, capable ofmanufacturing a pipe stock for seamless pipes by a piercer withoutcausing pipe inside surface defects resulting from overheating.

Further, the Non-Patent Document 1 discloses a technique capable ofperforming rolling, in the piercing and rolling of high Cr-high Nialloys, without causing inside surface scabs or two-piece cracks byincreasing the roll cross angle and the roll feed angle.

Patent Document 1: U.S. Pat. No. 4,168,188,

Patent Document 2: U.S. Pat. No. 4,245,698,

Patent Document 3: International Patent Publication Pamphlet No. WO03/044239,

Patent Document 4: Japanese Laid-Open Patent Publication No. 11-302801,

Patent Document 5: Japanese Laid-Open Patent Publication No.2000-301212,

Non-Patent Document 1: Tomio YAMAKAWA and Chihiro HAYASHI: CAMP-ISIJ,Vol. 6 (1993), 364.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

An alloy with Mo content of not more than 1.5% in the Patent Document 4among the alloys proposed in the Patent Documents 1 to 4, that is tosay, the alloy with Mo content of not more than 1.5% among the “highCr-high Ni alloys, excellent in stress corrosion cracking resistance”containing 20 to 35% of Cr and 25 to 50% of Ni, which are proposed asmaterials for oil wells and gas wells, has high hot workability, andcauses no flaws and cracks even if pierced and rolled by a piercer.Therefore, if this alloy is used as a steel stock, a pipe stock for analloy pipe can be manufactured with high productivity. Consequently,this alloy can be used as a material for oil wells and gas wells due toits extremely excellent economical properties.

However, the corrosion resistance of this alloy is not necessarilysatisfactory in an environment in which carbon dioxide partial pressureis raised to, for example, about 1013250 to 2026500 Pa (10 to 20 atm)because of the Mo content as low as not more than 1.5%, although it doeshave satisfactory corrosion resistance in an environment in which thehydrogen sulfide partial pressure of 101325 to 1013250 Pa (1 to 10 atm),a temperature of 150 to 250° C., and a carbon dioxide partial pressureof about 709275 Pa (7 atm).

On the other hand, the Ni base alloys and super austenitic stainlessalloys simultaneously containing Mo and/or W in large quantities, such avalue represented by the equation of Mo (%)+0.5W (%) exceeds 1.5%(hereinafter referred also to as “Mo equivalent value”), in addition tohigh contents of both Cr and Ni, which are proposed in the PatentDocuments 1 to 3, are excellent in corrosion resistance in a severe sourgas environment but too low in hot workability, so that the piercing androlling by a piercer thereof inevitably involved flaws or cracks in thepast.

Similarly, among the high Cr-high Ni alloys containing 20 to 35% of Crand 25 to 50% of Ni, which are proposed in the Patent Document 4, analloy with a Mo content exceeding 1.5% (hereinafter also referred to “Moequivalent value exceeding 1.5%) is excellent in corrosion resistance ina severe sour gas environment, but too low in hot workability, so thatthe piercing and rolling by a piercer thereof inevitably involved flawsor cracks in the past.

That is to say, in the manufacturing of pipe stocks of austeniticmaterials by piercing and rolling with a piercer, inside surface flawsor two-piece cracks resulting from fusion remarkably occurred even whenusing austenitic stainless steels such as SUS 316, SUS 321 and SUS 347regulated by JIS as steel stocks. Accordingly, when an austenitic alloysimultaneously containing Mo and W in large quantities exceeding 1.5% interms of Mo equivalent value, in addition to high contents of Cr and Ni,which is further harder to work than the above-mentioned austeniticstainless steels, is pierced and rolled with a piercer by the generalmethod, the occurrence of flaws or cracks could not be avoided asdescribed above.

Consequently, the said pipe stocks for high-strength, high-corrosionresistance seamless pipes for oil wells and gas wells of various highCr-high Ni alloys, with Mo equivalent value exceeding 1.5%, which haveextremely satisfactory corrosion resistance in the sour gas environment,have been ordinarily manufactured by a hot extrusion process such as theUgine-Sejournet method.

However, the hot extrusion process is not suitable for a manufacturingof pipe stocks for large diameter pipes or sufficiently long pipes. Thepipe stocks manufactured by the hot extrusion process, such as theUgine-Sejournet method, consequently could not respond to industrialdemands for increased productivity of oil or gas and also meet the lowcost of manufacturing alloy pipes to be used in oil wells and gas wells.

The pipe stocks for large diameter pipes or sufficiently long pipes canbe manufactured, for example, by hot forging using a transverse press.However, the alloys which have high contents of both Cr and Ni andsimultaneously containing Mo and W in large quantities exceeding 1.5% interms of Mo equivalent value, are hard-to-work materials with extremelylow hot workability, and so, the forgeable temperatures thereof arelimited to a narrow range. Therefore, the industrial mass production ofthe pipe stocks for large diameter pipes or sufficiently long pipes byhot forging using these alloys is also problematic because of thenecessity of repetition of heating and forging and the resultingextremely poor productivity and yield.

Accordingly, for various alloys having high contents of both Cr and Ni,simultaneously containing Mo and W in large quantities exceeding 1.5% interms of Mo equivalent value and having extremely satisfactory corrosionresistance in the sour gas environment, it is highly demanded toefficiently manufacture pipe stocks for the large diameter pipes orsufficiently long pipes by piercing and rolling with a piercer at a lowcost on an industrial scale, similarly to the cases of carbon steels andlow alloy steels, and further martensitic stainless steels such asso-called “13%-Cr steel”.

However, the “hard-to-work materials”, which are intended by the methodfor piercing with a piercer proposed by the Patent Document 5, aresimply those lower in the deformation resistance than the stainlesssteels as described in paragraph [0004] thereof. Therefore, theabove-mentioned high Cr-high Ni austenitic alloys simultaneouslycontaining Mo and W in large quantities, exceeding 1.5% in terms of Moequivalent value, with respect to Ni, Mo and W each of which is anelement increasing the deformation resistance, particularly, theaustenitic alloys, including not less than 15% Cr and more than 45% Niand further simultaneously containing Mo and W in large quantities,exceeding 1.5% in terms of Mo equivalent value, are not taken intoaccount by the said method in the Patent Document 5. Further, the saidmethod for piercing with a piercer only comprises adjusting a billetheating temperature in association with a piercing rate by a piercer,thereby performing piercing and rolling while controlling the billetinternal temperature to be lower than an overheat temperature.

The “overheat temperature” intended by the method for piercing with apiercer of the Patent Document 5 is 1260 to 1310° C. The “overheattemperature” means a temperature at which the material causesintergranular fusion. In order to apply the method for piercing with apiercer, as shown in FIG. 5 of the Patent Document 5, even to a materiallower in deformation resistance than a stainless steel, it is necessaryto control the billet heating temperature to 1180° C. maximum, which islower than that in the conventional rolling of a carbon steel, a lowalloy steel and a martensitic stainless steel. Similarly, as shown inFIG. 5 of the same, the piercing rate is also 300 mm/sec maximum, andmust be reduced to about a half or less of the conventional one even inthe case of the highest 300 mm/sec. For example, manufacturing of a pipestock of 8 m length requires about 27 seconds which is about twice theconventional one.

In the technique disclosed by the Patent Document 5, the billet heatingtemperature must be adjusted in association with the piercing rate by apiercer to prevent the billet inner part from being heated to theoverheat temperature or higher during piercing and rolling. For example,as shown in the said FIG. 5, if the billet heating temperature is raisedto about 1180° C., the piercing rate must be set to an extremely lowcondition of about 50 mm/sec, which cannot be endured through theindustrial mass production. If the piercing rate is set to about 300mm/sec, the manufacturing can be performed with efficiency at about halfthe conventional one as described above, but the billet heatingtemperature, as shown in the said FIG. 5, must be set to an extremelylow temperature of about 1060° C. Therefore, the manufacturing of pipestocks of austenitic alloys with high deformation resistance whichinclude not less than 15% Cr and more than 45% Ni and furthersimultaneously contains Mo and W in large quantities exceeding 1.5% interms of Mo equivalent value, needs a piercing performance far more thanthat of a general piercer, and thus needs an extremely large powersource for the piercer.

The technique disclosed in the Non-Patent Document 1 describes,concretely, that rolling can be performed without inside surface scabsor two-piece cracks by setting the roll cross angle to not less than 10°and the roll feed angle to not less than 14° in the piercing of a25Cr-35Ni-3Mo alloy and a 30Cr-40Ni-3Mo alloy, and by setting the rollfeed angle to not less than 16° with a roll cross angle of 10° orsetting the roll feed angle to not less than 14° with a roll cross angleof 15° in the piercing of a 25Cr-50Ni-6Mo alloy.

However, a general piercer used in a seamless steel pipe manufacturingfactory, which has been built for the purpose of piercing and rollingcarbon steels and low alloy steels, and further martensitic stainlesssteels such as so-called “13%-Cr steel”, has a roll cross angle of about0 to 10° and a roll feed angle of about 7 to 14°.

Accordingly, the replacement of the piercer to having a large roll crossangle and roll feed angle as proposed in the Non-Patent Document 1 forthe purpose of piercing and rolling of a high Cr-high Ni alloynecessitates a huge cost, and is not realistic.

Consequently, the piercing and rolling by a piercer of pipe stocks forlarge diameter and sufficiently long pipes of austenitic Ni base alloysincluding not less than 15% Cr and more than 45% Ni and furthersimultaneously containing Mo and W in large quantities, exceeding 1.5%in terms of Mo equivalent value, has never been performed on anindustrial mass production scale.

In other words, there are no pipe stocks obtained by the piercing androlling the austenitic Ni base alloys including not less than 15% Cr andmore than 45% Ni and further simultaneously containing Mo and W in largequantities exceeding 1.5% in terms of Mo equivalent value on anindustrial mass production scale.

In order to solve the above-mentioned problems, the present inventorsmade detailed examinations for the occurrence state of inside surfaceflaws in the piercing and rolling by a piercer of hard-to-work Ni basealloys of high Cr-high Ni series, particularly, austenitic Ni basealloys including not less than 15% Cr and more than 45% Ni and furthersimultaneously containing Mo and W in large quantities exceeding 1.5% interms of Mo equivalent value, from the point of microstructure change ofthe materials. As the result, the following findings (a) to (d) wereobtained.

(a) Inside surface fracture flaws caused in the Ni base alloys of highCr-high Ni series can be roughly classified into three groups asfollows:

(1) Two-piece cracks resulting from the intergranular fusion involved bywork heat generation on the high temperature side;

(2) Inside surface scabs resulting from high deformation resistance;and,

(3) Inside surface cracks and scabs on both the inside and outsidesurface resulting from the sigma phase formation in a low temperatureregion caused by a drop in temperature.

(b) The two-piece cracks resulting from the intergranular fusion of theabove-mentioned (1) is remarkable when solidification segregation ofelements which comprise the material to be pierced and rolled,particularly, the solidification segregation of C, P and S, is present.The solidification segregation state of C, P and S which greatly dependson the composition balance of Fe, Ni, Cr, Mo and the like, namely, thestate of the intergranular fusion can be evaluated by the value ofT_(GBm) represented by the following equation (1) in the austenitic Nibase alloys, including not less than 15% Cr and more than 45% Ni, andfurther simultaneously containing Mo and W in large quantities exceeding1.5% in terms of Mo equivalent value. When the value of T_(GBm) is notless than 1300 piercing and rolling property is enhanced, and so, thetwo-piece cracks can be suppressed in the piercing and rolling by apiercer:T _(GBm)=1380−5000P−100S−4400C  (1).

(c) The deformation resistance in hot working of the material changesmainly depending on the contents of Ni, N, Mo and W, and a material withhigher deformation resistance more likely causes the inside surfacescabs of above-mentioned (2). The occurrence state of the said insidesurface scabs can be evaluated by the value of P_(sr) represented by thefollowing equation (2) in the austenitic Ni base alloys, including notless than 15% Cr and more than 45% Ni, and further simultaneouslycontaining Mo and W in large quantities exceeding 1.5% in terms of Moequivalent value. When the value of P_(sr) is not more than 200, theinside surface scabs can be suppressed in the piercing and rolling by apiercer:P _(sr)=Ni+10(Mo+0.5W)+100N  (2).

(d) When a billet temperature falls, among the elements which comprisethe material to be pierced and rolled, the composition balance of Ni, N,Cr, Mo and W mainly has great influence on the formation of the sigmaphase. In the said austenitic Ni base alloys including not less than 15%Cr and more than 45% Ni, and further simultaneously containing Mo and Win large quantities, exceeding 1.5% in terms of Mo equivalent value, theinside surface cracks and the scabs on both the inside and outsidesurface resulting from the formation of the sigma phase of theabove-mentioned (3) are remarkable when the sigma phase is formed at1000° C. The said inside surface cracks and the said scabs on both theinside and outside surface can be evaluated by the value of P_(σ)represented by the following equation (3). When the value of P_(σ) isnot less than 0, the said inside surface cracks and the said scabs onboth the inside and outside surface can be suppressed in the piercingand rolling by a piercer:P _(σ)=(Ni−50)+10(N−0.1)−2(Cr−25)−5(Mo+0.5W−6)+12  (3).

Each element symbol in the above equations (1) to (3) represents thecontent by mass % of the element concerned.

The present inventors further made various examinations for theconditions of the piercing and rolling billets of the austenitic Ni basealloys including not less than 15% Cr and more than 45% Ni and furthersimultaneously containing Mo and W in large quantities exceeding 1.5% interms of Mo equivalent value, by a piercer. As a result, the followingfindings (e) and (f) were obtained.

(e) In the austenitic Ni-base alloys in which upper limit values of thecontents of C, P and S are controlled to 0.04%, 0.03% and 0.01%,respectively, the value of T_(GBm) represented by the said equation (1)is set to not less than 1300, the two-piece cracks resulting from theintergranular fusion can be easily suppressed by increasing a pipeexpansion ratio H represented by the ratio of an outer diameter of apipe stock to a diameter of a steel stock billet.

(f) In addition to the condition of the above-mentioned (e), the valueof fn represented by the following equation (4), that is a relationalequation of the pipe expansion ratio H and contents of P and S containedin a Ni base alloy is set to not more than 0.3, whereby the two-piececracks resulting from the intergranular fusion in the piercing androlling by a piercer can be perfectly prevented:fn={P/(0.025H−0.01)}² +{S/(0.015H−0.01)}²  (4).

In the above equation (4), P and S represent the contents, by mass %, ofP and S in a pipe stock, respectively, and H represents the pipeexpansion ratio represented by the ratio of the outer diameter of a pipestock to the diameter of a steel stock billet.

The present invention has been accomplished on the basis of theabove-mentioned findings. It is an objective of the present invention toprovide Ni base alloy pipe stocks of high Cr-high Ni seriessimultaneously containing Mo and W in large quantities exceeding 1.5% interms of Mo equivalent value, and pierced and rolled by a piercer, whichhave excellent corrosion resistance in a sour gas environment inaddition to excellent mechanical properties, such as strength andductility, and manufacturing methods thereof, particularly, Ni basealloy pipe stocks, including not less than 15% Cr and more than 45% Ni,and further simultaneously containing Mo and W in large quantities,exceeding 1.5% in terms of Mo equivalent value, and manufacturingmethods thereof. It is another objective of the present invention toprovide Ni base alloy seamless pipes, excellent in mechanical propertiesand the corrosion resistance in a sour gas environment, which aremanufactured using the above-mentioned pipe stocks.

MEANS FOR SOLVING THE PROBLEM

The gists of the present invention are Ni base alloy pipe stocks shownin the following (1) to (7), methods for manufacturing Ni base alloypipe stocks shown in (8) and (9), and a Ni base alloy seamless pipeshown in (10).

(1) A Ni base alloy pipe stock, having a chemical compositioncomprising, by mass %, C: not more than 0.04%, Si: not more than 0.50%,Mn: 0.01 to 6.0%, P: not more than 0.03%, S: not more than 0.01%, Cr: 15to 30%, Ni: more than 45% to not more than 60%, Mo: 0 to 18%, W: 0 to36%, with Mo(%)+0.5W (%): more than 1.5% to not more than 18%, Cu: 0.01to 1.5%, Al: not more than 0.10% and N: 0.0005 to 0.20%, and the balancebeing substantially Fe, with values of T_(GBm), P_(sr) and P_(σ)represented by the following equations (1) to (3) being not less than1300, not more than 200, and not less than 0, respectively, and moreoverbeing subjected to piercing and rolling by a Mannesmann piercing androlling mill:T _(GBm)=1380−5000P−100S−4400C  (1),P _(sr)=Ni+10(Mo+0.5W)+100N  (2),P _(σ)=(Ni−50)+10(N−0.1)−2(Cr−25)−5(Mo+0.5W−6)+12  (3),wherein each element symbol in the equations (1) to (3) represents thecontent by mass % of the element concerned.

(2) The Ni base alloy pipe stock according to the above (1), wherein Mnis 0.01 to 1.0%.

(3) A Ni base alloy pipe stock according to the above (1) or (2), whichfurther contains one or more elements selected from among V: 0.001 to0.3%, Nb: 0.001 to 0.3%, Ta: 0.001 to 1.0%, Ti: 0.001 to 1.0%, Zr: 0.001to 1.0% and Hf 0.001 to 1.0% in lieu of part of Fe.

(4) A Ni base alloy pipe stock according to any one of the above (1) to(3), which further contains B: 0.0001 to 0.015% in lieu of part of Fe.

(5) A Ni base alloy pipe stock according to any one of the above (1) to(4), which further contains Co: 0.3 to 5.0% in lieu of part of Fe.

(6) A Ni base alloy pipe stock according to any one of the above (1) to(5), which further contains one or more elements selected from among Mg:0.0001 to 0.010%, Ca: 0.0001 to 0.010%, La: 0.0001 to 0.20%, Ce: 0.0001to 0.20%, Y: 0.0001 to 0.40%, Sm: 0.0001 to 0.40%, Pr: 0.0001 to 0.40%and Nd: 0.0001 to 0.50% in lieu of part of Fe.

(7) The Ni base alloy pipe stock according to any one of the above (1)to (6), which has the chemical composition according to any one of thesaid (1) to (6), with the value of fn represented by the followingequation (4) being not more than 0.3:fn={P/(0.025H−0.01)}² +{S/(0.015H−0.01)}²  (4),wherein P and S represent contents, by mass %, of P and S in the pipestock, respectively, and H represents the pipe expansion ratiorepresented by the ratio of the outer diameter of the pipe stock to thediameter of a steel stock billet.

(8) A method for manufacturing a Ni base alloy pipe stock, comprisingpiercing and rolling a billet, which satisfies the chemical compositionsaccording to any one of the above (1) to (6), by use of a Mannesmannpiercing and rolling mill.

(9) The method for manufacturing a Ni base alloy pipe stock according tothe above (8), wherein the piercing and rolling by the Mannesmannpiercing and rolling mill is performed in a condition where the value offn represented by the following equation (4) is not more than 0.3:fn={P/(0.025H−0.01)}² +{S/(0.015H−0.01)}²  (4),wherein P and S represent contents, by mass %, of P and S in the pipestock, respectively, and H represents the pipe expansion ratiorepresented by the ratio of the outer diameter of the pipe stock to thediameter of the steel stock billet.

(10) A Ni base alloy seamless pipe, manufactured by use of the Ni basealloy pipe stock according to any one of the above (1) to (7) or by useof the Ni base alloy pipe stock manufactured by the method according tothe above (8) or (9).

The above-mentioned inventions (1) to (7) related to the Ni base alloypipe stocks, inventions (8) and (9) related to the methods formanufacturing a Ni base alloy pipe stock, and the invention (10) relatedto the Ni base alloy seamless pipe are referred to as “the presentinvention (1)” to “the present invention (10)”, respectively, orcollectively referred to as “the present invention”.

EFFECT OF THE INVENTION

Oil country tubular goods and line pipes and various structural membersof nuclear power plants and chemical industrial plants, which aremanufactured using the Ni base alloy pipe stocks of the presentinvention as steel stocks are excellent in corrosion resistance in asour gas environment, and also have excellent mechanical properties suchas strength and ductility. Therefore, the Ni base alloy pipe stocks ofthe present invention can be used as pipe stocks for oil country tubulargoods and line pipes, and also can be used as pipe stocks for variousstructural members of nuclear power plants and chemical industrialplants. Further, since the Ni base alloy pipe stocks of the presentinvention are obtained by piercing and rolling with a piercer, largediameter pipes or sufficiently long pipes can be easily manufacturedusing them as steel stocks, and the industrial demand forhigh-efficiency and low cost development of oil wells and gas wells canbe sufficiently satisfied.

BEST MODE FOR CARRYING OUT THE INVENTION

All of the requirements of the present invention will next be describedin detail.

(A) Chemical Composition of Ni Base Alloy

In the following description, the symbol “%” for the content of eachelement represents “% by mass”.

C: not more than 0.04%

An excessive content of C remarkably increases the amount of M₂₃C₆ typecarbides, resulting in a deterioration of ductility and toughness of thealloy. Particularly, a content of C exceeding 0.04% causes a remarkabledeterioration of ductility and toughness. Therefore, the content of C isset to not more than 0.04%. The content of C is preferably reduced to0.02% or less. When the content of C is controlled to 0.010% or less,not only the ductility and toughness but also the corrosion resistancecan be remarkably improved.

The “M” in the “M₂₃C₆ type carbides” means metal elements such as Mo,Fe, Cr, W and the like in combination.

A high content of C causes solidification segregation which reduces theintergranular fusion temperature of the Ni base alloy, resulting in adeteriorated piercing and rolling property by a piercer. Therefore, thecontent of C must be set to an amount in which the value of T_(GBm)represented by the said equation (1) satisfies not less than 1300 fromthe balance with contents of P and S described later.

Si: not more than 0.50%

Excessive Si promotes the formation of the sigma phase, causing adeterioration of ductility and toughness. Particularly, a content of Siexceeding 0.50% makes it difficult to suppress the inside surface cracksand the scabs on both the inside and outside surface resulting from thesigma phase formation in the piercing and rolling by a piercer even ifthe value of P_(σ) represented by the said equation (3) is not less than0. Therefore, the content of Si is set to not more than 0.50%. If thecontent of Si is reduced to 0.10% or less, the grain boundaryprecipitation of the carbides can be suppressed to largely improve theductility, toughness and corrosion resistance.

Mn: 0.01 to 6.0%

Mn has a desulfurizing effect. In order to ensure this effect, thecontent of Mn must be set to not less than 0.01%. However, a content ofMn exceeding 6.0% promotes the formation of the M₂₃C₆ type carbides, andso, the corrosion resistance may be deteriorated. Therefore, the contentof Mn is set to 0.01 to 6.0%. A content of Mn exceeding 1.0% promotesthe formation of the sigma phase, and may cause the inside surfacecracks and the scabs on both the inside and outside surface resultingfrom the sigma phase formation in piercing and rolling by a piercer evenif the value of P_(σ) represented by the said equation (3) is not lessthan 0. Accordingly, the content of Mn is set more preferably to 0.01 to1.0% and further more preferably to 0.01 to 0.50%.

P: not more than 0.03%

P is an impurity which is generally inevitably included. If it ispresent in an alloy in large quantities, not only the hot workabilitybut also the corrosion resistance generally deteriorates. Particularly,a content of P exceeding 0.03% makes a remarkable deterioration of hotworkability and corrosion resistance. Therefore, the content of P is setto not more than 0.03%. The content of P is set further preferable tonot more than 0.01%.

Since a high content of P causes solidification segregation, theintergranular fusion temperature of the Ni base alloy falls, and thisresults in a deterioration of the piercing and rolling property by apiercer. Therefore, the content of P must be set to an amount in whichthe value of T_(GBm) represented by the said equation (1) satisfies notless than 1300 from the balance with the content of C described aboveand the content of S described below.

S: not more than 0.01%

S is also an impurity which is generally inevitably included. If it ispresent in an alloy in large quantities, not only the hot workabilitybut also the corrosion resistance generally deteriorates. Particularly,a content of S exceeding 0.01% makes a remarkable deterioration of hotworkability and corrosion resistance. Therefore, the content of S is setto not more than 0.01%. The content of S is set more preferably to notmore than 0.005%.

Since a high content of S causes solidification segregation, theintergranular fusion temperature of the Ni base alloy falls, and thisresults in a deterioration of the piercing and rolling property by apiercer. Therefore, the content of S must be set to an amount in whichthe value of T_(GBm) represented by the said equation (1) satisfies notless than 1300 from the balance with the contents of C and P describedabove.

Cr: 15 to 30%

Cr, with Mo, W and N, has the effect of improving the corrosionresistance and strength of an alloy. This effect can be remarkablyobtained with a content of Cr of not less than 15%. However, if thecontent of Cr exceeds 30%, the hot workability of the alloydeteriorates. Therefore, the content of Cr is set to 15 to 30%. Thecontent of Cr is set more preferably to 21 to 27%.

In the present invention, in order to suppress the inside surface cracksand the scabs on both the inside and outside surface resulting from thesigma phase formation, the content of Cr must be set to an amount inwhich the value of P_(σ) represented by the said equation (3) satisfiesnot less than 0 from the balance with the contents of Ni, Mo, W and Ndescribed later.

Ni: more than 45% to not more than 60%

Ni, with N, has the effect of stabilizing the austenite matrix, and itis an essential element for including elements having a strengtheningeffect and a corrosion resisting effect such as Cr, Mo and W in the Nibase alloy. Ni also has an effect of suppressing the formation of thesigma phase. Each of the effects described above can be easily obtainedwhen the content of Ni exceeds 45%. On the other hand, a large amount ofadditional Ni causes an excessive increase of alloy cost, and if thecontent of Ni exceeds 60%, the cost extremely increases. Therefore, thecontent of Ni is set to more than 45% to not more than 60%. The contentof Ni is set more preferably to 50 to 60%.

In the present invention, in order to suppress the excessive rise ofdeformation resistance and to suppress the inside surface scabs, thecontent of Ni must be set to an amount in which the value of P_(sr)represented by the said equation (2) satisfies not more than 200 fromthe balance with the contents of Mo, W and N described later. In orderto suppress the inside surface cracks and the scabs on both the insideand outside surface resulting from the sigma phase formation, thecontent of Ni must be set to an amount in which the value of P_(σ)represented by the said equation (3) satisfies not less than 0 from thebalance with the content of Cr described above and the contents of Mo, Wand N described later.

Mo: 0 to 18%, W: 0 to 36%, Mo (%)+0.5W (%): more than 1.5% to not morethan 18%

Both Mo and W have the effect of enhancing the strength of an alloy incoexistence with Cr, and further the effect of remarkably improvingcorrosion resistance, particularly, pitting resistance. In order toensure these effects, Mo and/or W must be included in an amountexceeding 1.5% in terms of value represented by the expressionMo(%)+0.5W(%), namely, in terms of Mo equivalent value. However, a Moequivalent value exceeding 18% causes a significant deterioration ofmechanical properties such as ductility and toughness. Mo and W do notneed a composite addition, and can be added simply so that the Moequivalent value is within the above range. Therefore, the content of Mois set to 0 to 18%, and the content of W is set to 0 to 36%, and thevalue of Mo(%)+0.5W(%) is set to more than 1.5% to not more than 18%.

In the present invention, in order to suppress the excessive rise ofdeformation resistance to suppress the inside surface scabs, thecontents of Mo and W and the Mo equivalent value must be set to amountsso that the value of P_(sr) represented by the said equation (2)satisfies not more than 200 from the balance with the content of Nidescribed above and the content of N described later. In order tosuppress the inside surface cracks and the scabs on both the inside andoutside surface resulting from the sigma phase formation, the contentsof Mo and W and the Mo equivalent value must be set to amounts so thatthe value of P_(σ) represented by the said equation (3) satisfies notless than 0 from the balance with the contents of Cr and Ni describedabove and the content of N described later.

Cu: 0.01 to 1.5%

Cu is an element effective for improving the corrosion resistance in asour gas environment and, particularly, it has the effect of highlyenhancing the corrosion resistance, in coexistence with Cr, Mo and W, ina sour gas environment where S (sulfur) is observed as a separatedelement. This effect is obtained with a content of Cu of not less than0.01%. However, a content of Cu exceeding 1.5% may cause a deteriorationof ductility and toughness. Therefore, the content of Cu is set to 0.01to 1.5%. The content of Cu is set more preferably to 0.5 to 1.0%.

Al: not more than 0.10%

Al is the most harmful element which promotes the formation of the sigmaphase. Particularly, a content of Al exceeding 0.10% makes it difficultto suppress the inside surface cracks and the scabs on both the insideand outside surface resulting from the sigma phase formation in thepiercing and rolling by a piercer even if the value P_(σ) represented bythe said equation (3) is not less than 0. Therefore, the content of Alis set to not more than 0.10%. The content of Al is set more preferablyto not more than 0.06%.

N: 0.0005 to 0.20%

N is one of important elements in the present invention, and with Ni, ithas the effect of stabilizing the austenite matrix and the effect ofsuppressing the formation of the sigma phase. The above-mentionedeffects can be obtained with a content of N of not less than 0.0005%.However, excessive addition of N may cause a deterioration of toughness,and particularly a content exceeding 0.20% may cause a remarkabledeterioration of toughness. Therefore, the content of N is set to 0.0005to 0.20%. The content of N is set more preferably to 0.0005 to 0.12%.

In the present invention, in order to suppress the excessive rise ofdeformation resistance and to suppress the inside surface scabs, thecontent of N must be set to an amount in which the value of P_(sr)represented by the said equation (2) satisfies not more than 200 fromthe balance with the contents of Ni, Mo and W described above. Moreover,in order to suppress the inside surface cracks and the scabs on both theinside and outside surface resulting from the sigma phase formation, thecontent of N must be set to an amount in which the value of P_(σ)represented by the said equation (3) satisfies not less than 0 from thebalance with the contents of Cr, Ni, Mo and W described above.

Fe: substantial balance

Fe has the effect of ensuring the strength of an alloy and also reducingthe content of Ni in order to decrease the cost of the alloy. Therefore,in the alloys of steel stocks for the Ni base alloy pipe stocks of thepresent invention, a substantial balance of the element Fe is included.

Value of T_(GBm): not less than 1300

As described above, among the inside surface flaws which are present inthe Ni base alloys of the high Cr-high Ni series, the two-piece cracksresulting from the intergranular fusion involved by work heat generationon the high temperature side is remarkable, when the solidificationsegregation of elements which comprise the material to be pierced androlled, particularly the solidification segregation of C, P and S ispresent. In the austenitic Ni base alloys, including not less than 15%Cr and more than 45% Ni, and further simultaneously containing Mo and Win large quantities, exceeding 1.5% in terms of Mo equivalent value, thestate of the intergranular fusion can be evaluated by the value ofT_(GBm), represented by the said equation (1). When the value of T_(GBm)is not less than 1300, the two-piece cracks can be suppressed in thepiercing and rolling by a piercer, therefore, the value of T_(GBm) isset to not less than 1300. The value of T_(GBm) is set more preferablyto not less than 1320.

Value of P_(sr): not more than 200

As described above, among the inside surface flaws which are present inthe hard-to-work Ni base alloys of the high Cr-high Ni series,particularly in the austenitic Ni base alloys, including not less than15% Cr and more than 45% Ni, and further simultaneously containing Moand W in large quantities, exceeding 1.5% in terms of Mo equivalentvalue, the inside surface scabs resulting from high deformationresistance can be evaluated by the value of P_(sr), represented by thesaid equation (2). When the value of P_(sr) is not more than 200, theinside surface scabs can be suppressed in the piercing and rolling by apiercer, therefore, the value of P_(sr) is set to not more than 200. Thevalue of P_(sr) is set more preferably to not more than 150.

Value of P_(σ): not less than 0

Among the inside surface flaws which are present in the Ni base alloysof the high Cr-high Ni series, particularly, in the austenitic Ni basealloys, including not less than 15% Cr and more than 45% Ni, and furthersimultaneously containing Mo and W in large quantities, exceeding 1.5%in terms of Mo equivalent value, the inside surface cracks and the scabson both the inside and outside surface resulting from the sigma phaseformation in a low temperature region involved by a temperature drop canbe evaluated by the value of P_(σ), represented by the said equation(3). When the value of P_(σ) is not less than 0, the inside surfacecracks and the scabs on both inside and outside surface can besuppressed in the piercing and rolling by a piercer, therefore, thevalue of P_(σ) is set to not less than 0. The value of P_(σ) is set morepreferably to not less than 3.0.

Accordingly, the chemical compositions of the alloy as the steel stockfor the Ni base alloy pipe stock of the present invention (1) wasregulated to include elements of from C to N in the above-mentionedranges, and the balance substantially being Fe, with the value ofT_(GBm) being not less than 1300, the value of P_(sr) being not morethan 200, and the value of P_(σ) being not less than 0.

In the Ni base alloy pipe stock of the present invention (2), thecontent of Mn is particularly regulated from 0.01 to 1.0% in thecomposition of alloy as the steel stock for the Ni base alloy pipe stockof the present invention (1).

The alloys as steel stocks for the Ni base alloy pipe stocks of theprevent invention can selectively contain, in addition to theabove-mentioned components, one or more of elements of each groupdescribed below as occasion demands:

(i) One or more elements selected from among V: 0.001 to 0.3%, Nb: 0.001to 0.3%, Ta: 0.001 to 1.0%, Ti: 0.001 to 1.0%, Zr: 0.001 to 1.0% and Hf:0.001 to 1.0%;

(ii) B: 0.0001 to 0.015%;

(iii) Co: 0.3 to 5.0%; and

(iv) One or more elements selected from among Mg: 0.0001 to 0.010%, Ca:0.0001 to 0.010%, La: 0.0001 to 0.20%, Ce: 0.0001 to 0.20%, Y: 0.0001 to0.40%, Sm: 0.0001 to 0.40%, Pr: 0.0001 to 0.40% and Nd: 0.0001 to 0.50%.That is to say, one or more elements of the four groups (i) to (iv) canbe added thereto as optional additive elements.

The optional additive elements are described as follows:

(i) V: 0.001 to 0.3%, Nb: 0.001 to 0.3%, Ta: 0.001 to 1.0%, Ti: 0.001 to1.0%, Zr: 0.001 to 1.0% and Hf 0.001 to 1.0%

Each of V, Nb, Ta, Ti, Zr and Hf, if added, has the effect of remarkablyenhancing the corrosion resistance in a sour gas environment where S(sulfur) is observed as a separated element. Further, it forms MC typecarbides (M means any one element of V, Nb, Ta, Ti, Zr and Hf or acombination thereof) to effectively stabilize C, and also has the effectof enhancing the strength.

In order to ensure the above-mentioned effects, the content of eachelement of V, Nb, Ta, Ti, Zr and Hf is preferably set to not less than0.001%. However, if the contents of V and Nb exceed 0.3%, and thecontents of Ta, Ti, Zr and Hf exceed 1.0%, their independent carbidesare precipitated in large quantities, causing a deterioration ofductility and toughness.

Therefore, if V, Nb, Ta, Ti, Zr and Hf are added, the respectivecontents are preferably set to 0.001 to 0.3% for V, 0.001 to 0.3% forNb, 0.001 to 1.0% for Ta, 0.001 to 1.0% for Ti, 0.001 to 1.0% for Zr,and 0.001 to 1.0% for Hf.

From the above reason, the chemical compositions of the alloy as thesteel stock for the Ni base alloy pipe stock of the present invention(3) is regulated to contain, in lieu of part of Fe of the Ni base alloyin the present invention (1) or (2), one or more elements selected fromamong V: 0.001 to 0.3%, Nb: 0.001 to 0.3%, Ta: 0.001 to 1.0%, Ti: 0.001to 1.0%, Zr: 0.001 to 1.0%, and Hf 0.001 to 1.0%.

In the alloy as the steel stock for the Ni base alloy pipe stock of thepresent invention (3), further preferable content ranges of theelements, if added, are 0.10 to 0.27% for V, 0.03 to 0.27% for Nb, 0.03to 0.70% for Ta, 0.03 to 0.70% for Ti, 0.03 to 0.70 for Zr, and 0.03 to0.70% for Hf.

The above-mentioned V, Nb, Ta, Ti, Zr and Hf can be added alone or incombination of two or more thereof.

(ii) B: 0.0001 to 0.015%

B, if added, has the effect of refining precipitates and austenite grainsize. In order to definitely obtain the said effect, the content of B ispreferably set to not less than 0.0001%. However, excessive addition ofB may cause a deterioration of hot workability by the formation of lowmelting point compounds, and a content thereof exceeding 0.015%,particularly, can make a remarkable deterioration of hot workability.Therefore, the content of B, if added, is preferably set to 0.0001 to0.015%.

From the above reason, the chemical compositions of the alloy as thesteel stock for the Ni base alloy pipe stock of the present invention(4) is regulated to contain B: 0.0001 to 0.015% in lieu of part of Fe ofthe Ni base alloy in any one of the present inventions (1) to (3).

In the alloy of the steel stock for the Ni base alloy pipe stock of thepresent invention (4), a further preferable content range of B, ifadded, is 0.0010 to 0.0050%.

(iii) Co: 0.3 to 5.0%

Co, if added, has the effect of stabilizing austenite. In order toensure the said effect, the content of Co is preferably set to not lessthan 0.3%. However, excessive addition of Co causes excessive rise ofalloy cost, and a content of Co exceeding 5.0%, particularly, makes thecost increase excessive, therefore, the content of Co, if added, ispreferably set to 0.3 to 5.0%.

From the above reason, the chemical compositions of the alloy as thesteel stock for the Ni base alloy pipe stock of the present invention(5) is regulated to contain Co: 0.3 to 5.0%, in lieu of part of Fe ofthe Ni base alloy in any one of the present inventions (1) to (4).

In the alloy of the steel stock for the Ni base alloy pipe stock of thepresent invention (5), a further preferable content range of Co, ifadded, is 0.35 to 4.0%.

(iv) Mg: 0.0001 to 0.010%, Ca: 0.0001 to 0.010%, La: 0.0001 to 0.20%,Ce: 0.0001 to 0.20%, Y: 0.0001 to 0.40%, Sm: 0.0001 to 0.40%, Pr: 0.0001to 0.40% and Nd: 0.0001 to 0.50%

Each of Mg, Ca, La, Ce, Y, Sm, Pr and Nd, if added, has the effect ofpreventing solidification cracks in ingot casting. They also have theeffect of suppressing a deterioration of ductility after a long-termuse.

In order to ensure the above effects, the content of each element of Mg,Ca, La, Ce, Y, Sm, Pr and Nd is set preferably to not less than 0.0001%.However, when the contents of Mg and Ca exceed 0.010%, the contents ofLa and Ce exceed 0.20%, the contents of Y, Sm and Pr exceed 0.40%, orthe content of Nd exceeds 0.50%, coarse inclusions are produced, causinga deterioration of toughness.

Therefore, the contents of Mg, Ca, La, Ce, Y, Sm, Pr and Nd, if added,are preferably set to 0.0001 to 0.010% for Mg, 0.0001 to 0.010% for Ca,0.0001 to 0.20% for La, 0.0001 to 0.20% for Ce, 0.0001 to 0.40% for Y,0.0001 to 0.40% for Sm, 0.0001 to 0.40% for Pr, and 0.0001 to 0.50% forNd.

From the above reason, the chemical compositions of the alloy as thesteel stock for the Ni base alloy pipe stock of the present invention(6) is regulated to contain, in lieu of part of Fe of the Ni base alloyin any one of the present inventions (1) to Invention (5), one or moreelements selected from among Mg: 0.0001 to 0.010%, Ca: 0.0001 to 0.010%,La: 0.0001 to 0.20%, Ce: 0.0001 to 0.20%, Y: 0.0001 to 0.40%, Sm: 0.0001to 0.40%, Pr: 0.0001 to 0.40%, and Nd: 0.0001 to 0.50%.

In the alloy of the steel stock for the Ni base alloy pipe stock of thepresent invention (6), preferable content ranges of the elements, ifadded, are 0.0010 to 0.0050% for Mg, 0.0010 to 0.0050% for Ca, 0.01 to0.15% for La, 0.01 to 0.15% for Ce, 0.01 to 0.15% for Y, 0.02 to 0.30%for Sm, 0.02 to 0.30% for Pr and 0.01 to 0.30% for Nd.

The above-mentioned Mg, Ca, La, Ce, Y, Sm, Pr and Nd can be added aloneor in combination of two or more thereof.

Oil country tubular goods and line pipes and various structural membersof nuclear power plants and chemical industrial plants, which aremanufactured using the Ni base alloy pipe stocks having the chemicalcompositions described above as steel stocks are excellent in corrosionresistance in a sour gas environment, and also have excellent mechanicalproperties such as strength and ductility. Therefore, when the Ni basealloy pipe stocks, having the above-mentioned chemical compositions areapplied to pipe stocks for oil country tubular goods and line pipes, andalso to pipe stocks for various structural members of nuclear powerplants and chemical industrial plants, significant durability and safetycan be improved. That is to say, that Ni base alloy pipe stocks areextremely favorable for the use of members which are exposed in theabove-mentioned environment.

(B) Manufacturing Method of the Ni Base Alloy Pipe Stock

Not only to obtain pipe stocks for various members which are excellentin mechanical properties such as strength and ductility, and also haveexcellent corrosion resistance in a sour gas environment, but also tosatisfy the industrial demand for high-efficiency and low costdevelopment of oil wells and gas wells, industrial mass production ofpipe stocks for large diameter pipes or sufficiently long pipes isneeded. The piercing and rolling by a piercer is suitable for suchindustrial mass production of pipe stocks for large diameter pipes orsufficiently long pipes.

However, as already described, it has been difficult in the past to massproduce Ni base alloy pipe stocks, particularly Ni base alloy pipestocks, including not less than 15% Cr and more than 45% Ni andsimultaneously containing Mo and W in large quantities exceeding 1.5% interms of Mo equivalent value, which are excellent in mechanicalproperties, such as strength and ductility, and in corrosion resistancein a sour gas environment and also suitable as steel stocks for oilcountry tubular goods and line pipes and various structural members ofnuclear power plants and chemical industrial plants, by piercing androlling with a piercer by the same method as in the case of carbonsteels and low alloy steels and further martensitic stainless steels,such as so-called “13%-Cr steel” (hereinafter referred to as “generalmethod”). This is attributable to the piercing and rolling by a piercerof such a high Cr-high Ni alloy with large Mo equivalent value by thegeneral method inevitably causes the occurrence of flaws or cracks.

On the other hand, in the Ni base alloys having the chemicalcompositions described in the above (A), the contents of elements offrom C to N are optimized, the value of T_(GBm) represented by the saidequation (1), the value of P_(sr) represented by the said equation (2),and the value of P_(σ) represented by the said equation (3), which allhave correlations with the two-piece cracks resulting from theintergranular fusion on the high temperature side in the piercing androlling by a piercer, the inside surface scabs resulting from highdeformation resistance, and the inside surface cracks and the scabs onboth the inside and outside surface resulting from the sigma phaseformation, are set to not less than 1300, to not more than 200, and tonot less than 0, respectively. Therefore, billets of the Ni base alloys,having the chemical compositions described in the above (A), can bepierced and rolled with a piercer by the general method while preventingall of the two-piece cracks, the inside surface scabs, and the insidesurface cracks and the scabs on both the inside and outside surfaceresulting from the sigma phase formation. Therefore, the pipe stockswhich have satisfactory surface properties can be obtained.

Accordingly, the present invention (8) can respond to the industrialdemand for industrial mass-production of large diameter pipes orsufficiently long pipes by piercing and rolling the billets of Ni basealloys, having the compositions described in the above (A), with apiercer. And the Ni base alloy pipe stocks according to the presentinventions (1) to (6) are regulated to have the chemical compositionsdescribed in the above (A) and to be pierced and rolled by a piercer.

The pipe stocks manufactured by the method of the present invention (8),namely, the pipe stocks obtained by piercing and rolling the billetshaving the chemical compositions of the above (A) by a piercer havesatisfactory surface properties in which all of the two-piece cracks,the inside surface scabs, and inside surface cracks and the scabs onboth the inside and outside surface resulting from the sigma phaseformation are suppressed. Therefore, the Ni base alloy pipe stocks ofthe present inventions (1) to (6) can sufficiently respond to theabove-mentioned industrial demand.

The piercing and rolling by a piercer of the billets having the chemicalcompositions described in the above (A) can be performed by the generalmethod.

That is to say, the piercing and rolling by a piercer can be performedin the same condition as in the case of carbon steels and low alloysteels, and further martensitic stainless steels such as so-called“13%-Cr steel”. Concretely, for example, the piercing and rolling can beperformed with a billet heating temperature of 1200 to 1300° C., a rollcross angle of 0 to 10°, a roll feed angle of 7 to 14°, a draft rate of8 to 14%, and a plug tip draft rate of 4 to 7%.

The draft rate and the plug tip draft rate are represented by thefollowing equations (5) and (6), respectively.Draft rate (%)={(Diameter of the steel stock−Gauge space of theroll)/Diameter of the steel stock}×100  (5),Plug tip draft rate (%)={(Diameter of the steel stock−Roll gap at theforemost end of the plug)/Diameter of the steel stock}×100  (6).

As described above, the piercing and rolling by a piercer of thebillets, having the chemical compositions described in the above (A),can be performed by the general method without providing any specialconditions. However, as already described, the pipe expansion ratio H,represented by the ratio of an outer diameter of the pipe stock to adiameter of the steel stock billet, is increased whereby the two-piececracks resulting from the intergranular fusion can be easily suppressed.Further, if the value of fn, presented by the said equation (4), is setto not more than 0.3, the two-piece cracks resulting from theintergranular fusion in the piercing and rolling by a piercer can beabsolutely prevented, even in the case of Ni base alloys including notless than 15% Cr and more than 45% Ni and simultaneously containing Moand W in large quantities exceeding 1.5% in terms of Mo equivalentvalue.

Therefore, in the present invention (9), the piercing and rolling by apiercer of billets of the Ni base alloys, having the chemicalcompositions described in the above (A), is performed with the value offn represented by the said equation (4) being set to not more than 0.3.Also the Ni base alloy pipe stock of the present invention (7) isregulated to have the chemical composition described in the above (A)with the value of fn represented by the said equation (4) satisfying notmore than 0.3, and also to be pierced and rolled by a piercer.

As described above, by increasing the value of the pipe expansion ratioH in the piercing and rolling by a piercer, the two-piece cracksresulting from the intergranular fusion can be easily suppressed.However, if the value of the pipe expansion ratio H exceeds 2, thephenomenon of the pipe stock becoming excessively swollen, and the steelstock protruding to a clearance between a roll and a disk or guide shoe,each of them is an outside surface regulating tool, and a fracture canbe easily caused, resulting in rolling troubles. Therefore, the upperlimit value of the pipe expansion ratio H is preferably set to 2. Whenthe lower limit value of the pipe expansion ratio H is less than 1, aplug or a mandrel, each of them is a tool for inside surface working,must be reduced in the outer diameter, since the outer diameter of theresulting pipe stock becomes smaller than the diameter of the steelstock billet, which impractically causes erosion of the plug or curvingof the mandrel, due to insufficient heat capacity.

(C) Ni Base Alloy Seamless Pipe

The Ni base alloy seamless pipe manufactured by use of the Ni base alloypipe stock according to any one of the present inventions (1) to (7), orby use of the Ni base alloy pipe stock manufactured by the method of thepresent inventions (8) or (9) has satisfactory surface properties, andalso is excellent in mechanical properties and in the corrosionresistance in a sour gas environment. Therefore, such seamless pipes aresuitable to be used as oil country tubular goods or line pipes, and asvarious structural members of nuclear power plants and chemicalindustrial plants.

Therefore, in the present invention (10), the Ni base alloy seamlesspipe is regulated to be manufactured using the Ni base alloy pipe stock,according to any one of the present inventions (1) to (7), or using theNi base alloy pipe stock manufactured by the method of the presentinventions (8) or Invention (9).

The Ni base alloy pipe stock according to any one of the presentinventions (1) to (7) or the Ni base alloy pipe stock manufactured bythe method of the present inventions (8) or (9) can be easilymanufactured into a desired Ni base alloy seamless pipe by working it bythe general method, for example, by expanding the diameter by use of anelongator, such as a mandrel mill, a plug mill, an Assel mill or a pushbench to reduce the wall thickness, and then by narrowing the outerdiameter by use of a reducing mill, such as a stretch reducing mill or asizing mill.

The present invention will be described in more detail in reference topreferred embodiments.

PREFERRED EMBODIMENT Example 1

Various kinds of alloys, having chemical compositions shown in Tables 1and 2, were melted by use of a 150 kg vacuum induction melting furnacein the ordinary manner, and casted to form ingots. In Tables 1 and 2,the alloys 1 to 23 are the alloys of the inventive examples in which thechemical compositions are within the range regulated by the presentinvention, and the alloys a to r are the alloys of comparative examplesin which the content of any one of the components is out of the rangeregulated by the present invention. Among the alloys of comparativeexamples, the alloys a and b correspond to conventional alloys (ASM UNSNos. N06255 and N10276, respectively).

[Table 1] TABLE 1 Chemical composition (% by mass) Balance: Fe andimpurities Alloy C Si Mn P S Cr Ni Mo W Mo + 0.5W Cu 1 0.004 0.12 0.140.008 0.0021 24.88 52.36 6.75 — 6.75 0.71 2 0.006 0.08 0.52 0.007 0.001525.03 53.28 7.05 — 7.05 0.15 3 0.007 0.02 0.10 0.007 0.0030 22.54 46.666.51 — 6.51 0.76 4 0.002 0.06 0.49 0.009 0.0018 21.80 46.92 6.14 — 6.141.12 5 0.008 0.14 0.48 0.003 0.0008 18.83 53.36 3.82 — 3.82 0.92 6 0.0060.07 0.45 0.003 0.0007 15.68 58.77 13.66  — 13.66  0.87 7 0.012 0.190.09 0.004 0.0021 15.21 57.21 12.22  2.54 13.49  0.94 8 0.011 0.03 0.120.006 0.0011 24.85 55.21 6.62 3.36 8.30 1.05 9 0.003 0.28 0.30 0.0110.0005 25.51 48.87 5.53 — 5.53 0.57 10 0.003 0.01 0.29 0.005 0.000726.89 56.68 2.38 8.44 6.60 0.08 11 0.005 0.01 0.10 0.008 0.0004 26.1252.11 — 12.26 6.13 0.44 12 0.007 0.13 0.33 0.008 0.0011 27.73 58.72 5.85— 5.85 0.75 13 0.009 0.08 0.15 0.005 0.0025 25.08 55.53 4.61 4.06 6.640.99 14 0.005 0.07 0.83 0.007 0.0008 25.16 54.45 6.28 4.43 8.50 0.36 150.011 0.14 0.12 0.002 0.0007 24.42 50.36 6.33 — 6.33 0.48 16 0.008 0.020.30 0.003 0.0015 24.67 49.86 7.91 0.57 8.20 0.82 17 0.008 0.32 0.320.007 0.0020 25.17 51.21 0.35 8.89 4.80 0.77 18 0.006 0.08 0.10 0.0100.0006 25.58 52.13 6.68 0.54 6.95 0.48 19 0.006 0.16 0.30 0.005 0.001325.61 50.18 6.11 — 6.11 0.62 20 0.014 0.01 0.14 0.002 0.0008 23.88 52.066.34 — 6.34 1.05 21 0.003 0.05 5.03 0.006 0.0008 25.30 52.38 7.11 — 7.110.81 22 0.006 0.08 4.11 0.005 0.0024 20.46 59.13 11.54  0.60 11.84  0.6223 0.004 0.11 2.06 0.002 0.0013 22.23 57.93 8.86 0.33 9.03 0.77 a 0.0130.41 0.62 0.015 0.0023 24.47 48.85 6.24 — 6.24 0.86 b 0.005 0.07 0.410.003 0.0007 15.82 63.34 15.53  3.66 17.36  * — c * 0.053  0.35 0.600.012 0.0015 22.41 48.40 6.65 — 6.65 0.94 d 0.008 * 0.84  0.59 0.0080.0027 23.06 51.86 7.14 — 7.14 * 1.89  e 0.013 0.31 1.53 0.014 0.004322.34 47.77 5.08 2.23 6.20 1.33 f 0.015 0.29 0.32 * 0.035  0.0009 24.4752.26 4.31 3.38 6.00 1.04 g 0.007 0.13 0.47 0.009 * 0.0102  26.12 50.337.96 — 7.96 0.99 h 0.004 0.33 0.35 0.011 0.0041 * 14.38  47.79 — 12.456.23 1.05 i 0.015 0.30 0.66 0.013 0.0027 * 32.55  58.84 0.23 2.86 1.661.42 j 0.012 0.38 0.42 0.008 0.0050 25.31 * 42.81  8.11 — 8.11 0.88 k0.008 0.31 0.68 0.012 0.0028 24.88 48.63 * 18.89   — * 18.89   1.02 l0.007 0.35 0.42 0.007 0.0019 16.12 47.88 7.16 25.34 * 19.83   0.61 m0.009 0.28 0.67 0.005 0.0022 28.42 51.13 9.61 1.01 10.12  * 2.04  n0.011 0.44 0.38 0.011 0.0016 25.08 52.08 4.38 — 4.38 1.22 o 0.010 0.120.15 0.010 0.0014 20.97 46.66 7.63 1.75 8.51 0.31 p 0.013 0.05 0.330.008 0.0018 21.11 48.83 1.12 — * 1.12  0.43 q 0.006 0.43 0.77 0.0110.0015 24.82 * 30.61  0.89 — * 0.89  0.53 r 0.009 0.25 * 8.32  0.0090.0022 25.38 48.88 7.35 — 7.35 0.71A mark * indicate falling outside the conditions specified by thepresent invention.

[Table 2] TABLE 2 Chemical composition (% by mass) Balance: Fe andimpurities Value of Value of Value of Alloy Al N others T_(GBm) P_(sr)P_(σ) 1 0.083 0.002 — 1322.2 120.1  9.9 2 0.077 0.056 — 1318.5 129.4 9.5 3 0.069 0.007 V: 0.23 1313.9 112.5 10.1 4 0.085 0.004 Nb: 0.081326.0 108.7 13.7 5 0.073 0.003 — 1329.7  91.9 37.6 6 0.059 0.004 B:0.0032 1338.5 195.8  0.2 7 0.081 0.003 Mg: 0.0025 1307.0 192.4  0.4 80.052 0.007 Co: 2.01 1301.5 138.9  5.1 9 0.043 0.075 Nd: 0.11 1311.8111.7 12.0 10 0.088 0.124 — 1341.7 135.1 12.1 11 0.076 0.005 Zr0.04, B:0.0014 1318.0 113.9 12.3 12 0.062 0.143 Hf: 0.12, Co: 1.22, B: 0.00101309.1 131.5 16.4 13 0.074 0.076 V: 0.21, Nd: 0.10 1315.2 129.5 14.0 140.066 0.002 Hf: 0.13, Ca: 0.08 1322.9 139.6  2.7 15 0.081 0.003 V: 0.18,Nd: 0.07 1321.5 114.0 10.9 16 0.073 0.008 B: 0.0021, Nb: 0.08, Nd: 0.121329.7 132.6  0.6 17 0.048 0.012 Ta: 0.24, Co: 2.12 1309.6 100.4 18.0 180.052 0.025 Co: 0.46, Y: 0.13, B: 0.0025 1303.5 124.1  7.5 19 0.0440.003 V: 0.15, B: 0.0030, Co: 0.51, Ca: 0.0033 1328.5 111.6  9.4 200.067 0.007 — 1308.3 116.2 13.7 21 0.140 0.003 V: 0.12 1336.7 123.8  7.322 0.110 0.004 Nd: 0.04 1328.4 177.9  0.1 23 0.080 0.008 — 1352.3 149.0 9.4 a 0.071 0.008 — * 1247.6  112.1  9.8 b * 0.220  0.024 Co: 1.231342.9 * 239.3  * −13.9   c 0.077 0.004 — * 1086.7  115.3 11.4 d 0.0650.015 — 1304.5 124.8 11.2 e 0.072 0.011 — * 1252.4  110.8 13.2 f 0.0890.021 — * 1138.9  114.4 14.5 g 0.090 0.005 — 1303.2 130.4 * −0.7  h0.074 0.013 — 1307.0 111.3 29.0 i 0.081 * 0.211  — * 1248.7   96.5 28.6j 0.066 0.084 — * 1286.7  132.3 * −6.5  k 0.083 0.035 — * 1284.5  *241.0  * −54.2   l 0.092 0.008 — 1314.0 * 247.0  * −42.4   m 0.075 0.015— 1315.2 153.8 * −15.1   n * 0.187  0.123 — * 1276.4  108.2 22.3 o0.063 * 0.165  — * 1285.9  148.2  4.8 p 0.076 0.008 — * 1282.6   60.842.1 q 0.122 0.063 — * 1298.5   45.8 18.2 r 0.130 0.008 — * 1295.2 123.2  2.5A mark * indicate falling outside the conditions specified by thepresent invention.

Each of the ingots was soaked at 1200° C. for 2 hours, and then hotforged in the ordinary manner to produce, for each alloy, one billetwith a 85 mm in diameter, two billets 70 mm in diameter, and one billet55 mm in diameter for changing the pipe expansion ratio in the piercingand rolling. The finishing temperature of forging in each case was setto not lower than 1000° C.

Each of the thus-obtained billets was heated at 1250° C. for 1 hour, andpierced and rolled into a pipe stock of a size shown in Table 3 by useof a model mill with a pipe expansion ratio H of 1.09 to 1.74. In Table3, the relationship among the pipe expansion ratio, the billet size andthe pipe stock size is shown. The roll cross angle, roll feed angle,draft rate and plug tip draft rate that are piercing conditions of themodel mill, that is a piercing and rolling device, are shown in Table 4.

In Table 5, the value of fn represented by the said equation (4) of eachalloy is shown separately, for each pipe expansion ratio H of 1.09,1.36, 1.64 or 1.74 in the piercing and rolling.

[Table 3] TABLE 3 Billet Pipe stock Pipe stock Pipe diameter outerdiameter wall thickness expansion (mm) (mm) (mm) ratio H 85.0 93.0 6.51.09 85.0 115.5 5.5 1.36 70.0 115.0 6.5 1.64 55.0 95.5 5.5 1.74

[Table 4] TABLE 4 Piercing and rolling condition by model mill Rollcross angle 7 deg. Roll feed angle 9 deg. Draft rate 10.7% Plug tipdraft rate   6%

[Table 5] TABLE 5 fn value for following pipe expansion ratio H Alloy1.09 1.36 1.64 1.74 1 ** 0.324449   0.151884 0.087286 0.074042 20.220471 0.105872 0.061544 0.052343 3 ** 0.387872   0.168280 0.0932100.078383 4 ** 0.352564   0.170581 0.099487 0.084676 5 0.046118 0.0215420.012368 0.010489 6 0.042398 0.020155 0.011664 0.009910 7 0.1631380.068551 0.037338 0.031270 8 0.150991 0.073687 0.043137 0.036746 9 **0.412837   0.212381 0.127083 0.108784 10 0.096168 0.047933 0.0283130.024167 11 0.219049 0.112590 0.067348 0.057646 12 0.245089 0.1222980.072274 0.061696 13 0.239016 0.101188 0.055335 0.046388 14 0.1805430.090987 0.053991 0.046131 15 0.025595 0.011475 0.006461 0.005455 160.086046 0.036428 0.019921 0.016700 17 0.263871 0.122052 0.0697540.059094 18 ** 0.344992   0.176940 0.105747 0.090496 19 0.1259280.059028 0.033943 0.028796 20 0.029315 0.012862 0.007165 0.006033 210.136855 0.068417 0.040463 0.034547 22 0.226864 0.096657 0.0530370.044498 23 0.055355 0.022569 0.012091 0.010084 * a ** 0.887336   **0.439534   0.258948 0.220898 * b 0.042398 0.020155 0.011664 0.009910 * c** 0.539732   0.270803 0.160399 0.136994 * d ** 0.395873   0.1785110.100797 0.085152 * e ** 1.117238   0.511228 0.290697 0.245981 * f **4.136870   ** 2.134225   ** 1.278514   ** 1.094682   * g ** 2.852409  ** 1.102533   ** 0.572371   ** 0.473550   * h ** 0.823526   **0.365487   0.204771 0.172670 * i ** 0.748740   ** 0.360803   0.2100580.178714 * j ** 0.835082   ** 0.342250   0.183880 0.153475 * k **0.678364   ** 0.322485   0.186624 0.158559 * l 0.254199 0.1184460.067924 0.057589 * m 0.204048 0.088151 0.048721 0.040949 * n **0.470125   0.233738 0.137920 0.117695 * o ** 0.384672   0.1917320.113253 0.096668 * p 0.295433 0.141067 0.081797 0.069528 * q **0.462437   0.230872 0.136466 0.116499 * r ** 0.392244   0.1853740.106993 0.090849A mark * indicate the alloy whose chemical compositions are fallingoutside the conditions specified by the present invention.A mark ** indicate falling outside the conditions specified by thepresent inventions (7) and (9).

Each of the thus-obtained pipe stocks was examined for cracks and flaws,namely, for the two-piece cracks resulting from the intergranularfusion, the inside surface scabs, and the inside surface cracks and thescabs on both the inside and outside surface resulting from the sigmaphase formation.

The examination results for cracks and flaws are collectively shown inTable 6. The marks “oo”, “o” “Δ” and “x” in Table 6 mean that “no cracksor flaws were observed”, “small flaws were observed in spite of absenceof cracks”, “large flaws were observed in spite of absence of cracks”,and “cracks were observed”, respectively.

With respect to the alloys 1 to 23 and the alloys q and r whoseexamination results for cracks and flaws in the said pipe stocks includethe evaluation “oo”, those with a pipe expansion ratio H of 1.36 wererepresentatively subjected to a solution heat treatment holding at 1050°C. for 30 minutes followed by water cooling. Thereafter, an oblong steelstock 5 mm in thickness, 12 mm in width and 150 mm in length was cut offand cold rolled by the general method into a plate 3.5 mm in thickness,and this was used as a steel stock and examined for tensile propertiesand corrosion resistance.

That is to say, a tensile test piece with a diameter of 3 mm and a gaugelength of 15 mm was cut off from the above-mentioned 3.5 mm thick plateand subjected to a tensile test at room temperature in the atmosphere tomeasure the yield strength (YS) and the elongation (El).

A four-point bending corrosion test piece 10 mm in width, 2 mm inthickness and 75 mm in length, having a notch part with radius of 0.25mm, was produced from the 3.5 mm thick plate, and the corrosionresistance, namely, the stress corrosion cracking resistance in a sourgas environment in the following condition was evaluated.

Test solution: 20% NaCl-0.5% CH₃COOH,

Test gas: Hydrogen sulfide partial pressure 1013250 Pa-carbon dioxidepartial pressure 2026500 Pa (10 atm H₂S-20 atm CO₂),

Test temperature: 221° C.,

Dipping time: 1000 hours

Applied stress: 1×YS.

The tensile test results and the corrosion test results are collectivelyshown in Table 6. In Table 6, the marks “o” and “x” of the column ofcorrosion resistance (stress corrosion cracking resistance in sour gasenvironment) mean that no cracks were observed and that cracks wereobserved, respectively. The mark “-”, in the columns of tensileproperties and corrosion resistance for the alloys a to p, means that notest was carried out because of the absence of pierced and rolled pipestocks having the evaluation of “oo” for cracks and flaws.

[Table 6] TABLE 6 Cracks and flaws on the pipe Tensile propertiesCorrosion resistance stock for following pipe Yield strength Elongation(stress corrosion expansion ratio H [YS] [El] resistance in sour Alloy1.09 1.36 1.64 1.74 (MPa) (%) gas environment) 1 ∘ ∘∘ ∘∘ ∘∘ 896 24.3 ∘ 2∘∘ ∘∘ ∘∘ ∘∘ 902 25.7 ∘ 3 ∘∘ ∘∘ ∘∘ ∘∘ 913 26.3 ∘ 4 ∘∘ ∘∘ ∘∘ ∘∘ 885 25.0 ∘5 ∘∘ ∘∘ ∘∘ ∘∘ 937 24.7 ∘ 6 ∘∘ ∘∘ ∘∘ ∘∘ 1036 23.7 ∘ 7 ∘∘ ∘∘ ∘∘ ∘∘ 94026.3 ∘ 8 ∘ ∘∘ ∘∘ ∘∘ 893 27.3 ∘ 9 ∘∘ ∘∘ ∘∘ ∘∘ 911 25.7 ∘ 10 ∘∘ ∘∘ ∘∘ ∘∘924 26.3 ∘ 11 ∘∘ ∘∘ ∘∘ ∘∘ 897 26.7 ∘ 12 ∘∘ ∘∘ ∘∘ ∘∘ 883 27.0 ∘ 13 ∘∘ ∘∘∘∘ ∘∘ 908 26.7 ∘ 14 ∘∘ ∘∘ ∘∘ ∘∘ 926 24.7 ∘ 15 ∘∘ ∘∘ ∘∘ ∘∘ 981 25.3 ∘ 16∘∘ ∘∘ ∘∘ ∘∘ 1013 23.0 ∘ 17 ∘ ∘∘ ∘∘ ∘∘ 945 29.7 ∘ 18 ∘∘ ∘∘ ∘∘ ∘∘ 992 22.7∘ 19 ∘ ∘∘ ∘∘ ∘∘ 896 26.0 ∘ 20 ∘∘ ∘∘ ∘∘ ∘∘ 870 23.3 ∘ 21 ∘∘ ∘∘ ∘∘ ∘∘ 98622.5 ∘ 22 ∘∘ ∘∘ ∘∘ ∘∘ 1121 24.1 ∘ 23 ∘∘ ∘∘ ∘∘ ∘∘ 933 23.8 ∘ * a x ∘ ∘ ∘— — — * b x x ∘ ∘ — — — * c x x x ∘ — — — * d x x x ∘ — — — * e x x x ∘— — — * f x x x ∘ — — — * g x x x ∘ — — — * h Δ ∘ ∘ ∘ — — — * i x x ∘ ∘— — — * j Δ Δ Δ Δ — — — * k Δ Δ Δ Δ — — — * l Δ Δ Δ Δ — — — * m x x x ∘— — — * n x Δ ∘ ∘ — — — * o x x x ∘ — — — * p x x ∘ ∘ — — — * q ∘ ∘∘ ∘∘∘∘ 861 25.3 x * r x ∘∘ ∘∘ ∘∘ 949 21.3 xA mark “—” in the columns of tensile properties and corrosion resistancemeans that no tests were carried out because of absence of pierced androlled pipe stock having the evaluation of “∘∘” for cracks and flaws.A mark * indicate the alloy whose chemical compositions are fallingoutside the conditions specified by the present invention.

As is apparent from Table 6, when the alloys 1 to 23, which are the Nibase alloys according to the present invention, are used, theexamination results for cracks and flaws after piercing and rolling was“oo” in most cases, with a slight number of cases with “o”. That is tosay, these alloys are excellent in surface property with no cracks andonly small flaws.

Further, the examination results for tensile properties and corrosionresistance in the use of the alloys 1 to 23 were satisfactory. That isto say, these alloys are excellent in strength and toughness with alarge YS exceeding 800 MPa and a large elongation exceeding 20%, andalso excellent in the corrosion resistance in the said severe sour gasenvironment.

Consequently, it is apparent that seamless pipes excellent in thecorrosion resistance in a sour gas environment in addition to excellentmechanical properties can be mass-produced on an industrial scale byusing the pipe stocks obtained by piercing and rolling billets of the Nibase alloys according to the present invention by the general method.

In contrast to this, the examination results for cracks and flaws afterpiercing and rolling in the use of the alloy q, that is an alloy ofcomparative example, were “oo” or “o”. That is to say, it is excellentin surface properties with no cracks and only small flaws. However, thecorrosion test result thereof was “x”, which apparently shows that thecorrosion resistance in the said severe sour gas environment was poor.

The examination results for cracks and flaws after piercing and rollingin the use of the alloy r, that is an alloy of comparative example, were“oo” or “x”. That is to say, it shows that cracking may have takenplace. And the corrosion resistance test result thereof was “x”, whichapparently shows that the corrosion resistance in the said severe sourgas environment was also poor.

In the use of the alloys a to p, which are the alloys of comparativeexamples, the examination results for cracks and flaws after piercingand rolling were “o” at most. That is to say, the piercing and rollingthereof caused large flaws although no cracks was caused. Therefore, itis apparent that, even if the pipe stocks obtained by piercing androlling billets of such alloys by the general method are used, seamlesspipes excellent in the corrosion resistance in a sour gas environment inaddition to excellent mechanical properties cannot be mass-produced onan industrial scale.

Example 2

A Ni base alloy having a chemical composition, equivalent to that of thealloy 1 in Table 1, was melted by use of real equipment, and thenbloomed and rolled to produce five billets 147 mm in diameter. Thechemical composition of this Ni base alloy is shown in Table 7.

[Table 7] TABLE 7 Chemical composition (% by mass) Balance: Fe andimpurities C Si Mn P S Cr Ni Mo W Mo + 0.5W Cu Al N 0.008 0.11 0.130.008 0.0015 24.89 52.53 6.24 — 6.24 0.83 0.090 0.007 Value of T_(GBm)Value of P_(sr) Value of P_(σ) 1304.7 115.7 12.6

Each billet was heated to 1230° C. and made into a pipe by use of realequipment in a condition shown in Table 8 to produce a pipe stock withouter diameter of 235 mm and thickness of 15 mm. Since the pipeexpansion ratio H in piercing and rolling of this case is 1.5, the valueof fn represented by the said equation (4) is 0.099028. As a piercerplug suitable for piercing and rolling of Ni base alloys, one made of amaterial consisting of 0.5% Cr-1.0% Ni-3.0% W series with a tensilestrength at 900° C. of 90 MPa and a total scale thickness before use of600 μm was used.

[Table 8] TABLE 8 Piercing and rolling condition by real equipment Rollcross angle 7 deg. Roll feed angle 9 deg. Draft rate 10.7% Plug tipdraft rate   6%

The five pipe stocks were examined for the cracks and flaws, namely, forthe two-piece cracks resulting from the intergranular fusion, the insidesurface scabs, and the inside surface cracks and the scabs on both theinside and outside surface resulting from the sigma phase formation.Consequently, each pipe stock could be confirmed to have satisfactorysurface properties free from cracks and flaws.

Each of the said five pipe stocks was cold drawn at 30% in terms of thereduction in the cross-sectional area and then carried out a solutionheat treatment of heating to 1120° C. followed by water cooling, andfurther subjected to a cold drawing of 30% in terms of the reduction inthe cross-sectional area.

The same tensile test pieces and corrosion test pieces as in Example 1were cut off from the longitudinal direction of the thus-obtained pipes,and examined for tensile properties and corrosion resistance.

That is to say, a tensile test piece with a diameter of 3 mm and a gaugelength of 15 mm was cut off from the longitudinal direction of eachpipe, and subjected to a tensile test at room temperature in theatmosphere to measure the yield strength (YS) and the elongation (El).

A four-point bending corrosion test piece 10 mm in width, 2 mm inthickness and 75 mm in length, having a notch part with radius of 0.25mm, was produced from the said pipe, and the corrosion resistance,namely, the stress corrosion cracking resistance in a sour gasenvironment in the following condition was evaluated.

Test solution: 20% NaCl-0.5% CH₃COOH,

Test gas: Hydrogen sulfide partial pressure 1013250 Pa-carbon dioxidepartial pressure 2026500 Pa (10 atm H₂S-20 atm CO₂),

Test temperature: 221° C.,

Dipping time: 1000 hours

Applied stress: 1×YS.

The tensile test results and corrosion resistance test results arecollectively shown in Table 9. In Table 9, the mark “o” of the column ofcorrosion resistance (stress corrosion cracking resistance in sour gasenvironment) means that no cracks were observed.

[Table 9] TABLE 9 Tensile properties Corrosion resistance Yield strengthElongation (stress corrosion [YS] [El] resistance in sour Pipe (MPa) (%)gas environment) 1 983 24.3 ∘ 2 969 23.5 ∘ 3 986 24.8 ∘ 4 964 21.6 ∘ 5961 25.5 ∘

As is apparent from Table 9, each pipe has satisfactory strength andductility and further extremely satisfactory corrosion resistance.

Although only some exemplary embodiments of the present invention havebeen described in detail above, those skilled in the art will readilyappreciated that many modifications are possible in the exemplaryembodiments without materially departing from the novel teachings andadvantages of the present invention. Accordingly, all such modificationsare intended to be included within the scope of the present invention.

INDUSTRIAL APPLICABILITY

The Ni base alloy pipe stocks of the present invention have excellentinside surface properties. Therefore, the pipe stocks can bemanufactured into seamless pipes of desired dimensions by working themby the general method, for example, by expanding the diameter by use ofan elongator, such as a mandrel mill, a plug mill, an Assel mill or apush bench to reduce the wall thickness, and then by narrowing the outerdiameter by use of a reducing mill, such as a stretch reducing mill or asizing mill. The resulting seamless pipes have excellent mechanicalproperties and moreover have excellent corrosion resistance in a sourgas environment, and thus, the Ni base alloy pipe stocks of the presentinvention can be used as pipe stocks for oil country tubular goods andline pipes and further as pipe stocks for various structural members ofnuclear power plants and chemical industrial plants. The Ni base alloypipe stocks can be easily mass-produced at a low cost by the method ofthe present invention.

1-19. (canceled)
 20. A Ni base alloy pipe stock, having a chemicalcomposition comprising, by mass %, C: not more than 0.04%, Si: not morethan 0.50%, Mn: 0.01 to 6.0%, P: not more than 0.03%, S: not more than0.01%, Cr: 15 to 30%, Ni: more than 45% to not more than 60%, Mo: 0 to18%, W: 0 to 36%, with Mo(%)+0.5W(%): more than 1.5% to not more than18%, Cu: 0.01 to 1.5%, Al: not more than 0.10% and N: 0.0005 to 0.20%,and the balance being substantially Fe, with values of T_(GBm), P_(sr)and P_(σ) represented by the following equations (1) to (3) being notmore than 1300, not more than 200 and not less than 0, respectively, andmoreover being subjected to piercing and rolling by a Mannesmannpiercing and rolling mill:T _(GBm)=1380−5000P−100S−4400C  (1),P _(sr)=Ni+10(Mo+0.5W)+100N  (2),P _(σ)=(Ni−50)+10(N−0.1)−2(Cr−25)−5(Mo+0.5W−6)+12  (3), wherein eachelement symbol in the equations (1) to (3) represents the content bymass % of the element concerned.
 21. The Ni base alloy pipe stockaccording to claim 20, wherein the content of Mn is 0.01 to 1.0% by mass%.
 22. A Ni base alloy pipe stock according to claim 20, which furthercontains an element or elements of one or more groups selected from thegroups (a) to (d) listed below in lieu of part of Fe: (a): one or moreselected from among V: 0.001 to 0.3%, Nb: 0.001 to 0.3%, Ta: 0.001 to1.0%, Ti: 0.001 to 1.0%, Zr: 0.001 to 1.0% and Hf: 0.001 to 1.0% by mass%; (b): B: 0.0001 to 0.015% by mass %; (c): Co: 0.3 to 5.0% by mass %;(d): one or more selected from among Mg: 0.0001 to 0.010%, Ca: 0.0001 to0.010%, La: 0.0001 to 0.20%, Ce: 0.0001 to 0.20%, Y: 0.0001 to 0.40%,Sm: 0.0001 to 0.40%, Pr: 0.0001 to 0.40% and Nd: 0.0001 to 0.50% by mass%.
 23. The Ni base alloy pipe stock according to claim 22, wherein thecontent of Mn is 0.01 to 1.0% by mass %.
 24. The Ni base alloy pipestock according to claim 20, which further has the value of fnrepresented by the following equation (4) being not more than 0.3:fn={P/(0.025H−0.01)}² +{S/(0.015H−0.01)}²  (4), wherein P and Srepresent contents, by mass %, of P and S in the pipe stock,respectively, and H represents the pipe expansion ratio represented bythe ratio of the outer diameter of the pipe stock to the diameter of asteel stock billet.
 25. The Ni base alloy pipe stock according to claim21, which further has the value of fn represented by the followingequation (4) being not more than 0.3:fn={P/(0.025H−0.01)}² +{S/(0.015H−0.01)}²  (4), wherein P and Srepresent contents, by mass %, of P and S in the pipe stock,respectively, and H represents the pipe expansion ratio represented bythe ratio of the outer diameter of the pipe stock to the diameter of asteel stock billet.
 26. The Ni base alloy pipe stock according to claim22, which further has the value of fn represented by the followingequation (4) being not more than 0.3:fn={P/(0.025H−0.01)}² +{S/(0.015H−0.01)}²  (4), wherein P and Srepresent contents, by mass %, of P and S in the pipe stock,respectively, and H represents the pipe expansion ratio represented bythe ratio of the outer diameter of the pipe stock to the diameter of asteel stock billet.
 27. The Ni base alloy pipe stock according to claim23, which further has the value of fn represented by the followingequation (4) being not more than 0.3:fn={P/(0.025H−0.01)}² +{S/(0.015H−0.01)}²  (4), wherein P and Srepresent contents, by mass %, of P and S in the pipe stock,respectively, and H represents the pipe expansion ratio represented bythe ratio of the outer diameter of the pipe stock to the diameter of asteel stock billet.
 28. A Ni base alloy seamless pipe, manufactured byuse of the Ni base alloy pipe stock according to claim
 20. 29. A Ni basealloy seamless pipe, manufactured by use of the Ni base alloy pipe stockaccording to claim
 21. 30. A Ni base alloy seamless pipe, manufacturedby use of the Ni base alloy pipe stock according to claim
 22. 31. A Nibase alloy seamless pipe, manufactured by use of the Ni base alloy pipestock according to claim
 23. 32. A Ni base alloy seamless pipe,manufactured by use of the Ni base alloy pipe stock according to claim24.
 33. A Ni base alloy seamless pipe, manufactured by use of the Nibase alloy pipe stock according to claim
 25. 34. A Ni base alloyseamless pipe, manufactured by use of the Ni base alloy pipe stockaccording to claim
 26. 35. A Ni base alloy seamless pipe, manufacturedby use of the Ni base alloy pipe stock according to claim
 27. 36. Amethod for manufacturing a Ni base alloy pipe stock, comprising piercingand rolling a billet, which satisfies the chemical compositionsaccording to claim 20, by use of a Mannesmann piercing and rolling mill.37. The method for manufacturing a Ni base alloy pipe stock according toclaim 36, wherein the piercing and rolling by the Mannesmann piercingand rolling mill is performed in a condition where the value of fnrepresented by the following equation (4) is not more than 0.3:fn={P/(0.025H−0.01)}² +{S/(0.015H−0.01)}²  (4), wherein P and Srepresent contents, by mass %, of P and S in the pipe stock,respectively, and H represents the pipe expansion ratio represented bythe ratio of the outer diameter of the pipe stock to the diameter of thesteel stock billet.
 38. A Ni base alloy seamless pipe, manufactured byuse of the Ni base alloy pipe stock manufactured by the method accordingto claim
 36. 39. A Ni base alloy seamless pipe, manufactured by use ofthe Ni base alloy pipe stock manufactured by the method according toclaim 37.